GB2142651A - Metal-working compositions - Google Patents

Abstract

A metal-working oil composition containing:- (A) one or more lube-oil components which are oils and fats, mineral oils or fatty acid esters; and (B) one or more polyetherpolyol dispersants which are made by adding alkylene oxides to polyalkylene- imines or -polyamines, alkyl- or alkylaryl-amines, or carboxylic acid amides, or their derivatives, e.g. polyetherpolyol derivatives having molecular weights of 300 to 600,000 and obtained by adding alkylene oxides to polyalkyleneimines. Incorporation of the polyetherpolyol permits, owing to its protective colloidal function, stable dispersion of the lube-oil component as large droplets in water and hence the resulting dispersion enjoys good circulation stability and withstands severe machining conditions.

Description

SPECIFICATION Metal-working Oil Composition i) Field of the Invention This invention relates to a novel metal-working oil composition, and more particularly to a metalworking oil composition containing a lube-oil component and a specific polyetherpolyol derivative.

ii) Description of the Prior Art Conventional metal-working oils which have generally been used are each obtained by adding lube-oil additives such as an oilness agent, extreme-pressure additive, rust preventive and/or antioxidant to a lube-oil component such as an oil, fat, mineral oil or fatty acid ester and then converting the resultant mixture into an o/w-type emulsion by means of an emulsifier. They are fed to metal-working parts, usually with concentrations of 1 to 20%. In the case of rolling a metal for example, it has however been attempted to increase, namely, speed up the rolling speed so as to achieve mass production, relying upon rapid advancement in rolling facilities and technology which has been achieved in recent years.Reflecting such an attempt, requirements for rolling oil such as lubricity, circulation stability, working efficiency and treatment rediness of waste water have become progressively severer. There is thus a strong standing desire for the development of a rolling oil which can satisfactorily meet such requirements. However, conventional rolling oils which make use of emulsifiers are accompanied by various drawbacks and are hence unable to fulfill such requirements. In the case of a conventional rolling oil relying upon an emulsifier, the rolling lubricity was controlled by changing the type and amount of the emulsifier in such a way that the amount of the oil which was to adhere on rollers and each workpiece, in other words, the plate-out quantity was either increased or decreased.In such an emulsifier-containing rolling oil as described above, there was a problem that the plate-out quantity and the circulation stability of the emulsion showed mutually-contradictory tendency, namely, the plate-out quantity to each workpiece is decreased and the lubricity is thus rendered insufficient if the stability of the emulsion is enhanced. If one tried to increase the plate-out quantity, the emulsion became unstable and developed various problems when circulated for its reuse.

Accordingly, conventional rolling oils making use of emulsifiers were accompanied by such drawbacks as mentioned above. Furthermore, still further improvements are also desired to the lubricity and working efficiency of other metal-working oils such as press-working oils and cutting oils.

The present inventors therefore carried out a research with a view toward solving the aforementioned drawbacks which conventional emulsion-type metal working oil had. As a result, it was succeeded to improve the above-described drawbacks by using a lube-oil component, which contained an oil, fat or wax having a melting point of 20 to 1 00 C, in combination with a specific hydrophilic dispersant (a water-soluble, anionic, polymer compound) in such a way that the lube-oil component was stably suspended and dispersed in a solid form in water at a temperature below the melting point but the resultant dispersion became unstable when fed to each working part, i.e., at a temperature above the melting point. A patent application has been already made on the above finding (see, Japanese Patent Application Laid-open No. 147593/1980).

Summary of the Invention The present inventors have conducted a further research, resulting in a finding of a metal-working oil composition which may be successfully employed for working metals under high shear conditions which are expected to encounter upon an actual application of the oil composition and under highspeed and high-pressure conditions which permit high working speeds and great rolling reductions, permits metal machining under severe cutting conditions, and facilitates such process control as excellent liquid circulation stability.

More specifically, the present inventors have found that (1) use of a lube-oil component and a specific polyetherpolyol derivative optionally in combination with an acidic phosphoric acid or boric acid permits, owing to the protective colloidal function of the polyetherpolyol derivative, stable dispersion of the lube-oil component as large droplets in water and hence the resulting dispersion enjoys good circulation stability; (2) when the metal-working oil composition is supplied to a working part and brought into contact with a metallic workpiece, oil droplets having large diameters form a thick and strong lubrication film over the metallic workpiece; (3) while circulated and reused for an extended period of time, large diameters can be stably maintained against shear forces produced by a stirrer in a tank and by a feed and circulation pump; and (4) combined use of boric acid or an organic or inorganic acidic phosphoric compound, which has conventionally been known as a compound having extreme-pressure effects, forms a lubricating film on the metal workpiece and hence achieve still higher lubricity. The present invention has been completed on the basis of the above-described finding.

Accordingly, the present invention provides a metal-working oil composition containing as essential components the following components (A) and (B): (A) one or more lube-oil components selected from the group consisting of oils and fats, mineral oils and fatty acid esters; and (B) one or more polyetherpolyoktype dispersant components (hereinafter called "polyetherpolyol compound" for the sake of brevity) selected from the following groups (a) to (d):: (a) polyetherpolyols and polyetherpolyol derivatives having molecular weights of 300 to 600,000 and obtained respectively by adding alkylene oxides to polyalkyleneimines and derivatives thereof containing 6 to 200 nitrogen atoms; (b) polyolpolyether derivatives obtained respectively by adding alkylene oxides to polyalkylene polyamine and derivatives thereof; (c) polyolpolyether derivatives obtained respectively by adding alkylene oxides to alkyl- and alkylaryl-amines and derivatives thereof and having molecular weights of 200 to 100,000; and (d) polyetherpolyol derivatives obtained respectively by adding alkylene oxides to carboxylic acid amides and derivatives thereof and having molecular weights of 200 to 100,000.

The present invention also provides a metal-working oil composition containing the above components (A) and (B) in combination with one or more compounds selected from (C) acidic phosphoric acids and boric acid.

Detailed Description of the Invention and Preferred Embodiments As the lube-oil component which is the component (A) of the metal-working oil composition according to this invention, may for example be mentioned a mineral oil such as spindle oil, machine oil, turbine oil or cylinder oil, an animal or vegetable oil or fat such as whale oil, beef tallow, hog fat, rape oil, castor oil, rice bran oil, palm kernel oil or coconut oil, or an ester between a fatty acid obtained from beef tallow, coconut oil, palm oil, castor oil or the like and an aliphatic primary alcohol containing 1 to 22 carbon atoms, ethylene glycol, neopentyl alcohol, pentaerythritol or the like. These components may be used singly. Alternatively, two of these components may also be used in combination.

Among the components (B) of this invention, the polyetherpolyol or its derivatives, which is the component (a), may be prepared by using a polyalkyleneimine having 6 to 200 nitrogen atoms or preferably 9 to 100 nitrogen atoms or its derivative as a starting material and adding an alkylene oxide thereto.

Here, polyethyleneimine or polypropyleneimine having 6 to 200 nitrogen atoms or the like may be mentioned as the polyalkyleneimine. Besides, there may also be mentioned a polyalkyleneimine obtained by addition-polymerizing ethyleneimine or propyleneimine with a substance containing an active hydrogen, such as an alcohol, phenol, amine, carboxylic acid or the like, so as to contain 6 to 200 nitrogen atoms or a polyalkyleneimine obtained by the ammonolysis or aminolysis of its corresponding dihalogenoalkane and having 6 to 200 nitrogen atoms.

For example, polyethyleneimine may be readily obtained by adding ethyleneimine to a polyethylenepolyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine or by polymerizing ethyleneimine usually in the presence of an acidic catalyst.

It is preferred that the polyalkyleneimine contains at least 5 moieties, each represented by the following formula (I), continuously in its molecule, at least one of the 5 moieties is a moiety represented by the following formula (II) and the polyalkyleneimine contains an OH and/or NH2 groups at at least one end thereof.

Since the above-described polyalkyleneimine has excellent chemical reactivity similar to ordinary amines, a variety of derivatives may be synthetically obtained therefrom. Some representative examples of the polyalkyleneimines will hereinafter be given: (a) Reaction products with aldehydes or ketones; (b) Reaction products with alkyl halides; (c) Reaction products with isocyanates or thioisocyanates; (d) Reaction products with compounds each of which contains an active double bond; (e) Reaction products with epoxy compounds or epihalohydrins; (f) Reaction products with cyanamides, quanidines or ureas; and (g) Reaction products with carboxylic acids, acid anhydrides or acyl halides.

As a matter of fact, the polyalkyleneimines inclusive of the above derivatives are those having 6 to 200 nitrogen atoms or preferably 9 to 100 nitrogen atoms and obtained using polyalkyleneimines or their derivatives.

Alkylene oxides, which are to be added to the above polyalkyleneimines, are ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like. It is preferable to copolymerize propylene oxide and ethylene oxide. When copolymerizing, they may be subjected to block copolymerization or random copolymerization. Either one of propylene oxide and ethylene oxide may be added to one of the polyalkyleneimines in advance. It is more preferable to subject them to block copolymerization. The addition of an alkylene oxide is carried out to such an extent that the resulting polyetherpolyol has a molecular weight in the range of 6,000 to 600,000 or preferably 10,000 to 300,000. Preferably, the polyetherpolyol contains ethylene oxide as an alkylene oxide at a concentration of 3 to 80 wt% or more, and preferably 10 to 50 wt% based on the polyetherpolyol.Such a polyetherpolyol can provide still better properties.

Furthermore, the following compounds may be mentioned as polyetherpolyol derivatives: a) Reaction products, each obtained by a reaction between a terminal hydroxyl group and an equimolar amount of an epihalohydrin.

Epichlorohydrin is generally used as the epihalohydrin. This reaction permits introduction of an epoxy group to an end owing to the utilization of a difference in reactivity between an epoxy group and a halogen.

b) Compounds, each of which has been obtained by cationizing nitrogen atoms contained in the moieties partly or in their entirety or neutralizing the nitrogen atoms partly or in their entirety with an organic or inorganic acid.

As the cationizing reagent, an alkyl halide of diethyl sulfate may be used. It is possible to use an alkylarylsulfonic acid, acetic acid, hydrochloric acid or the like as the acid. An organic acid is however preferred.

c) Compounds, each of which has been obtained by either carboxylakylating or sulfating hydroxyl groups of terminal groups partly or in their entirely; and salts of the compounds.

d) Compounds, each of which has been obtained by either esterifying with either boric acid or phosphoric acid hydroxyl groups of terminal groups partly or in their entirety; and salts of the compounds.

The esterification reaction, which is supposed to take place with boric acid, may be readily carried out through a dehydration reaction with boric acid or a reaction with boric anhydride. On the other hand, the esterification reaction, which is supposed to take place with phosphoric acid, may be conducted with ease through a reaction with phosphorus pentoxide.

Among the components (B), the polyetherpolyol compounds (b) to (d) are compounds known in the art. They may be prepared by methods known per se in the art. Exemplary polyalkylenepolyamines and their derivatives which are raw materials useful in the preparation of polyetherpolyol compounds (b) may include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, and their N-alkyl compounds containing alkyl groups which have 4 to 22 carbon atoms; and aminoethylethanolamine, and N-alkylpropylenediamines and Nalkylbutylenediamines containing alkyl groups which have 4 to 22 carbon atoms.Furthermore, illustrative alkyl- or alkylaryl-amines and their derivatives (c) may embrace mono- or dialkyl-amines containing 4 to 36 carbon atoms, cycloalkylamines containing 3 to 6 carbon atoms, alkylarylamines containing alkyl groups each of which have 4 to 36 carbon atoms and at least one phenyl group. As examples of the carboxylic acid amides (d), may be mentioned monocarboxylic acid amides, each containing 4 to 22 carbon atoms, and polymerized acid amides such as their dimeric acids and trimeric acids.

It is also possible to improve the lubricity further by adding a phosphoric acid compound or boric acid as the component (C) of this invention. Among such components (C), the following compounds may be used as phosphoric acid compounds: (i) phosphoric acid and phosphorous acid as well as thio compounds and ester compounds thereof; (ii) mono- and di-phosphoric acid esters containing respectively alkyl, akylaryl and aryl groups which contain individually at least one hydroxyl group as well as thio compounds thereof; (iii) mono- or di-phosphonic acids which contain respectively alkyl groups containing 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio compounds thereof, as well as derivatives thereof;; (iv) mono- or di-phosphinic acids which contain respectively alkyl groups having 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio compounds thereof, as well as derivatives thereof; and (v) mono-, di- and tri-phosphonic acids containing one or more nitrogen atoms.

The following compounds may be mentioned as specific examples of the phosphoric acid compounds. As phosphoric acid compounds (i), may be mentioned by way of example phosphoric acid, phosphorous acid, mono- or di-phosphoric acid esters between aliphatic alcohols containing 1 to 8 carbon atoms, alicyclic alcohols or aromatic alcohols and phosphoric acid as well as thio compounds of the mono- or di-phosphoric acid esters, and esters between the above alcohols and phosphorous acid and thio compounds of the esters. As an exemplary phosphoric acid compound (ii), may be mentioned 2-hydroxydipropyl phosphate.Illustrative of the phosphoric acid compounds (iii) may include phosphonic acids represented by the general formula:

wherein Ro and Ró mean individually an alkyl group having 1 to 8 carbon atoms, alkylaryl group or aryl group, for example, methylphosphonic acid containing 1 carbon atom, dimethylphosphonic acid to noctylphosphonic acid containing 8 carbon atoms, di-n-octylphosphonic acid, benzylphosphonic acid, 2ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid and hydroxyethanediphosphonic acid, as well as their thiophosphonic acids.Hydroxyethanediphosphonic compound is a compound represented by the following formula:

As exemplary phosphinic acid compounds (iv), may be mentioned phosphinic acids represented by the general formula:

wherein Ro and Ró have the same meanings as defined above, for example, methylphosphinic acid containing 1 carbon atom, dimethylphosphinic acid to n-octylphosphinic acid containing 8 carbon atoms, di-n-octylphosphinic acid, 2-ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid and dipehylphosphinic acid, as well as their thiophosphinic acids. As phosphoric acid compounds (v), may for example be mentioned hexamethylphosphoric mono- (or di-)amide and nitrilotrismethylenephosphonic acid.

Nitrilotrismethylenephosphonic acid is a compound represented by the following formula:

The metal-working oil composition of this invention may be prepared by mixing the above components. It is however preferred to limit their proportions within the following ranges, all based on the whole composition: the lube-oil component (A): 99.9 to 50 wt% (hereinafter referred to merely as %), especially 99.9 to 70%, the polyetherpolyol compound (B): 0.1 to 3%, especially 0.1 to 10%, and the acidic phosphoric acid or boric acid (C): 0.1 to 70%, especially 0.1 to 50%.

To the metal-working oil composition of this invention, it is feasible to add, besides the abovementioned components, a variety of known additives as needed, for example, a surfactant, rust preventive, oilness agent, extreme-pressure additive, antioxidant and the like.

The above-described various additives may, whenever necessary, be added respectively in amounts of 5%,0to2%,0to20%,0to3%andOto5%.

As surfactants, the following surfactants (1) to (14) may be mentioned by way of example: (1) Polyoxyethylenealkyl. and alkylaryl ethers, each having 6 to 22 carbon atoms, and the end carboxymethylated salts thereof; (2) Polyoxyethylenepolyoxypropylenealkyl and alkylaryl ethers, each having 6 to 22 carbon atoms; (3) Oxyethylene-oxypropylene block polymers; (4) The sorbitan and polyoxyethylenesorbitan esters of fatty acids having 10 to 1 8 carbon atoms; (5) Polyethylene glycol esters containing 10 to 18 carbon atoms; (6) Monofatty acid-glycerin esters having 10 to 18 carbon atoms; (7) Polyoxyethylenealkylamines containing 6 to 22 carbon atoms; (8) Salts of alkyl- and alkylaryl-sulfonic acids containing 6 to 22 carbon atoms; (9) Salts of alkyl- and alkylaryl-sulfuric acids containing 6 to 22 carbon atoms;; (10) Salts of sulfates of polyoxyethylenealkyl- and polyoxyethylenealkylaryl ethers containing 6 to 22 carbon atoms; (11) Salts of fatty acids containing 6 to 22 carbon atoms; (12) Alkylaminecarbonates containing 6 to 22 carbon atoms; (13) Alkyl- and Alkylaryl-ammonium salts containing 6 to 22 carbon atoms, and their derivatives; and (14) Ethyleneoxide and propyleneoxide addition products of ethylenediaminetetraacetic acid.

Among these surfactants, non-ionic surfactants are especially preferred.

As illustrative rust preventives, may be mentioned fatty acids such as alkenylsuccinic acids and their derivatives and oleic acid, esters such as sorbitan monooleate, and amines, and so on. Exemplary oilness agents may include higher fatty acids such as oleic acid and stearic acid, fatty acid esters which are derivatives of such fatty acids, dibasic acids such as dimeric acid and the like. On the other hand, phosphorus compounds such as tricresylphosphates and organometallic compounds such as zinc dialkyldithiophosphates may be mentioned as exemplary extreme-pressure additives. As illustrative antioxidants, may be mentioned phenolic compounds such as 2,4-di-t-butyl-p-cresol, aromatic amines such as phenyl-alpha-naphthylamine, etc.

The metal-working oil composition of this invention may be employed by either simply mixing the above-described various components upon actually using the metal-working oil composition or preparing it as a thick solution having a water content of up to about 80% in advance and then diluting same with water upon actually using the metal-working oil composition.

The thus-obtained metal working oil composition according to this invention can provide a metalworking oil which can afford relatively large droplets with a stable size distribution under such stirring conditions as having a high shear force, can exhibit high-lubricative property and shows small quality changes along the passage of time and excellent circulation stability. Besides, the above metal-working oil composition of this invention has such merits as will be described next. The polyetherpolyol compound useful in the practice of this invention has by itself such capacity as being rapidly adsorbed on liquid or solid particles to make the liquid or solid particles hydrophilic but has by itself little capacity of lowering the interfacial tension between water and oil so as to emulsify their mixture. Therefore, the lube-oil component is not emulsified.Compared with conventional metal-working oils making use of emulsifiers, the metal-working oil composition of this invention is thus advantageous in that it develops the so-called holding-in phenomenon, that is to absorb fouled oil mixed in during an actual rolling operation and foreign matter such as metal powder and the like, only to lowered extent and it always retains high lubricating characteristics as a clean metal-working oil. Owing to the function of the abovedescribed polyolpolyether compound, the metal-working oil composition of this invention has rendered the working environment cleaner and the treatment of waste water easier. Therefore, the metalworking oil composition of this invention has such an excellent feature that it can materialize a clean working environment which has not been achieved by any conventional rolling oils making use of emulsifiers.

Although the mechanism of action achieved owing to the use of the polyetherpolyol compound and the acidic phosphoric acid or boric acid in accordance with this invention has not been fully elucidated, they seem to act probably in the following manner. Namely, the polyetherpolyol compound which has been dissolved uniformly in a water layer adsorbs droplets of the lube-oil component, which droplets have been formed by mechanical shear forces, before the droplets begin to agglomerate. The polyetherpolyol compound then converts oil droplets into larger droplets in accordance with a sort of coagulation action. The resultant larger droplets are dispersed stably in water by the steric and electric, protective-colloidal action of the polyetherpolyol compound.This feature is different from that brought about by the water-soluble, anionic, polymer compound in Japanese Patent Application Laid-open No.

147593/1980, because the water-soluble, anionic, polymer compound has a weak coagulation action for oil droplets and the lube-oil component is stabilized still in the form of fine droplets owing to the protective colloidal action and the thus-divided fine oil droplets cannot be formed back into larger droplets.

In connection with making each working oil clean, namely, avoiding inclusion of fouled matters (the holding-in phenomenon) owing to the prevention of reduction to the protective action of the high molecular compound for oil droplets and the prevention of their surface tensions by the high molecular compound as well as the cleaning action of the high molecular compound for such fouled matters, the phosphoric acid compound or boric acid is believed to enhance the above effects.

The invention will hereinafter be described with reference to the following Examples.

EXAMPLE 1 Metal-working oil compositions respectively of the compositions given in Table 1-A to Table 1-C were prepared and their seizure-resistant loads were measured. Test results are given in Table 2.

By the way, all designations of % in the tables mean wt%. (Compositions) TABLE 1-A (%) Lube-Oil Component Metal- Compound Working Fatty Acids Forming Oil Derived Polyether- Polyether- Anti Compo- Beef from Beef polyol polyol salt Oxidant sition Tallow Tallow (Note: 1) (Note: 2) (Note: 3) Invention Product No.

1 96 2 (1)1 1 2 96.5 2 (2) 0.5 1 3 96.8 2 (3) 0.1 1 (4) 0.1 4 91 2 (1)5 1 (3)1 5 86 2 (1)10 (1)1 1 6 96.3 2 (2) 0.5 (2) 0.2 1 7 91 2 (3)2 (3)2 1 (4)2 8 86 2 (1)5 (3)1 1 (3)5 TABLE 1-8 (%) Lube-Oil Component Metal- Compound Working Mineral Forming Oil Oil Polyether- Polyether- Anti Compo- (Spindle Octyl Oleic polyol polyol Salt Oxidant sition Oil) Stearate Acid (Note: 1) (Note: 2) (Note: 3) Invention Product No.

9 73.5 20 5 (1)0.5 1 10 69 20 5 (4)5 1 11 68 20 5 (2) 3 1 (3)3 12 64 20 5 (1)5 1 (4)5 13 71.6 20 5 (1)2 (1)0.4 1 14 67 20 5 (4)5 (3)2 1 15 65.5 20 5 (2)4 (3)0.5 1 (3)4 16 72.7 20 5 (1) O.1 (2)0.2 1 (4)1 TABLE 1-C (%) Lube-Oil Component Metal- Compound Working Mineral Penta- Forming Oil Oil erythritol Polyether- Polyether- Anti Compo- (Cylinder Tetra- polyol polyol salt Oxidant sition Oil) oleate (Note: 1) (Note: 2) (Note: 3) Invention Product No.

17 74 20 (1)5 1 18 78.8 20 (3)0.2 1 19 69 20 (2)10 1 20 74 20 (2)4 1 (4)1 21 77.9 20 (1)1 (1)0.1 1 22 73.95 20 (2) 5 (3) 0.05 1 23 75.9 20 (2)3 (3)0.1 1 24 78.45 20 (2) 0.25 (2) 0.05 1 (4) 0.25 Comparative product No. 1: Lube-oil components: Beef tallow 95% Fatty acids derived from beef tallow 2 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Comparative product No. 2 Lube-oil component: Beef tallow 94% Fatty acids derived from beef tallow 2 Extreme-pressure additive (Note: 5) 1 Emulsifier (Note: 4) 2 Antioxidant 1 Comparative product No. 3: Lube-oil component: Mineral oil (cylinder oil) 77% Pentaerythritol tetraoleate 20 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Comparative product No. 4 Lube-oil component: Mineral oil (cylinder oil) 76% Pentaerythritol tetraoleate 20 Extreme-pressure additive (Note: 5) 1 Emulsifier (Note: 4) 2 Antioxidant (Note: 5) 1 Comparative product No. 5: Lube-oil component: Mineral oil (spindle oil) 72% Octyl stearate 20 Oleic acid 5 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Comparative product No. 6: Lube-oil component: Mineral oil (spindle oil) 71% Octyl stearate 20 Oleic acid 5 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Extreme-pressure additive (Note: 5) 1 Note: 1 Polyetherpolyols: (1) A polyetherpolyol obtained by adding, to polyethyleneimine, ethylene oxide in an amount of 20% based on the polyethyleneimine and converting the resultant addition product into a glycolic acid salt, and having a molecular weight of 50,000; (2) A polyetherpolyol obtained by adding, to polyethyleneimine, a 1:1 (by weight) mixture of ethylene oxide and propylene oxide in an amount of 50% based on the polyethyleneimine and having a molecular weight of 1 50,000; (3) A polyetherpolyol obtained by adding, to polyethyleneimine, a 1:1 (by weight) mixture of ethylene oxide and butylene oxide in an amount of 60% based on the polyethyleneimine; and (4) A polyetherpolyol obtained by adding, to polyalkylene(ethylene: propylene=4:1 )imine, a 3:1 (by weight ratio) mixture of ethylene oxide and propylene oxide in an amount of 30% based on the polyalkyleneimine and having a molecular weight of 200,000.

Note: 2 Compounds Forming Polyetherpolyol Salt (1) Phosphoric acid; (2) Triphenylphosphinic acid; and (3) Zinc diethyldithiophosphate.

Note: 3 Emulsifier: Polyoxyethylenenonyl Phenyl Ether (HLB=7.6) Note: 4 Antioxidant: 2,4-di-t-butyl-p-cresol Note: 5 Extreme-pressure Additive: Triphenylphosphite (Testing Method) The measurement of seizure-resistant loads was carried out in accordance with ASTM Standard D-3233 Pressure Resistant Loading Test (Falex Test). The preparation of each test sample was carried out by diluting each metal-working oil composition with water to a concentration of 3% and then mixing the resultant mixture at 10,000 rpm in a homogenizer. The coating of each test sample was effected by applying the above-mixed solution to a rotary pin, which was disposed centrally in a fixed block, at a spray rate of 50 ml/min. (a pressure of 0.5 kg/cm2) and a dispersion temperature of 500C bs means of a gear pump.

(Results) TABLE 2 Metal-working Seizure-resistant Oil Composition Load (Ibs.) Invention Product No.

1 1,750 2 2,000 3 2,000 4 1,750 5 2,000 6 2,250 7 2,000 8 2,250 9 1,750 10 1,750 11 1,750 12 2,000 13 1,750 14 1,750 15 2,000 16 1,750 17 1,750 18 1,750 19 1,750 20 1,750 21 1,750 22 2,000 23 1,750 24 1,750 Comparative Product No.

1 1,250 2 1,500 3 1,250 4 1,250 5 1,250 6 1,500 EXAMPLE 2 With respect to the metal-working oil compositions prepared in Example 1, their seizure loads were measured. Results are summarized in Table 3.

(Testing Method) The measurement of seizure loads was Film conducted inaccordance with Japanese Self-Defence Force Provisional Standard NDS XXK 2740, Oil Film Strength Testing Method (Soda's Four-Ball Testing Method). The preparation of each test sample was carried out by diluting each metal-working oil composition with water to a concentration of 3% and then mixing the resultant mixture at 1 0,000 rpm in a homogenizer.The Coating of each test sample was effected by applying the above-mixed solution upwardly through a gap formed centrally among three points of contact of three testing steel balls, which were fixed by a ball retainer, to a rotary steel ball, which assumed a position above the three balls, at a spray rate of 0.5 liter/min. (a pressure of 0.5 kg/cm2) and a sample solution temperature of 500C by means of a gear pump.

(Results) TABLE 3 Metal-working Seizing Load Oil Composition (Kg/cm2) Invention Product No.

1 10.5 2 10.5 3 11.5 4 11.0 5 11.5 6 12.0 7 12.5 8 11.5 9 9.0 10 8.5 11 8.5 12 9.5 13 9.5 14 9.5 15 9.0 16 9.5 17 9.0 18 8.5 19 8.0 20 8.5 21 8.5 22 9.5 23 9.5 24 8.5 Comparative Product No.

1 7.0 2 8.0 3 5.5 4 6.0 5 5.5 6 6.0 EXAMPLE 3 Test on Readiness of Treatment of Waste Water Each test solution (1 liter) prepared in the same manner as in Example 2 was added with 3 g of aluminum sulfate. The resulting mixture was stirred for 2 minutes, followed by an addition of Ca(OH)2 to adjust its pH to 7.0. The thus-prepared mixture was stirred for further 10 minutes. After allowing the resultant mixture to stand for 30 minutes, the supernatant was collected to measure its COD (in accordance with the KMnO4 method). Results are given in Table 4.

TABLE 4 Metal-working Oil Composition COD (ppm) Invention Product No.

1 222 2 216 3 195 4 128 5 292 6 311 7 365 8 195 9 229 10 320 11 395 12 420 13 211 14 265 15 190 16 180 17 244 18 316 19 410 20 298 21 255 22 301 23 425 24 266 Comparative Product No.

1 1,980 2 2,210 3 2,560 4 1,870 5 2,200 6 2,110 EXAMPLE 4 Metal-working oil compositions of the compositions given in Table 5-A to Table 5-C were prepared. Their seizure-resistent loads were measured in the same manner as in Example 1. Results are shown in Table 6.

(Composition) TABLE 5-A (%) Lube-Oil Component Compound Fatty Acids Forming Inven- Derived Polyether- Polyether- Anti tion Beef from Beef polyol polyol salt Oxidant Product Tallow Tallow (Note: 1) (Note: 2) (Note: 3) No.25 96 2 (1)1 1 1 No. 26 94 2 (2)3 3 1 No. 27 92 2 (3) 5 1 1 No. 28 96.4 2 (4) 0.2 1 (5) 0.2 No. 29 94.5 2 (6)2 (1)0.5 1 No.30 91 2 (7)5 (2)1 1 No.31 94 2 (1)1 (3)1 1 (3)1 No. 32 86 2 (5) 5 (4)1 1 (8) 5 TABLE 5-8 (%) Lube-Oil Component Compound Mineral Penta- Forming Inven- Oil erythritol Polyether- Polyether- Anti tion (Cylinder Tetra- polyol polyol salt Oxidant Product Oil) oleate (Note: 1) (Note: 2) (Note: 3) No. 33 78.5 20 (1)0.5 1 No. 34 77 20 (2)1 1 1 (6)1 No. 35 73 20 (3)5 5 1 (4)1 No. 36 76.5 20 (5)2 (1)0.5 1 No. 37 73 20 (7) 5 (2)1 1 No.38 75 20 (1)1 (3)1 1 (8)2 No. 39 71 20 (3)2 (4)2 1 (6)4 No. 40 73 20 (4) 5 (3)1 1 TABLE 5-C (%) Lube-Oil Component Compound Mineral Forming Inven- Oil Octyl Polyether- Polyether- Anti tion (Spindle Stea- Oleic polyol polyol Salt Oxidant Product Oil) rate Acid (Note: 1) (Note: 2) (Note: 3) No. 41 72 20 5 (1)2 2 1 No. 42 73 20 5 (2) 0.5 1 1 (4) 0.5 No. 43 72.5 20 5 (3)1 (1)0.5 1 No. 44 70 20 5 (5) 3 (2)1 1 No. 45 71.5 20 5 (6)2 (3)0.5 1 No. 46 72.5 20 5 (7)1 (4) 0.5 1 No. 47 70 20 5 (8)4 4 1 No. 48 73 20 5 (4) 1 1 The following compositions were used as comparative products: Comparative product No. 7: Lube-oil component: Beef tallow 95% Fatty acids derived from beef tallow 2 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) Comparative product No. 8: Lube-oil component: Mineral oil (cylinder oil) 77% Pentaerythritol tetraoleate 20 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Comparative product No. 9: Lube-oil component: Mineral oil (spindle oil) 72% Octyl stearate 20 Oleic acid 5 Emulsifier (Note: 4) 2 Antioxidant (Note: 3) 1 Note: 1 Polyetherpolyol compounds: (1) A polyetherpolyol compound obtained by adding 5 moles of propylene oxide to ethylenediamine, followed by an addition of 10 moles of ethylene oxide; (2) A polyetherpolyol compound obtained by adding 10 moles of ethylene oxide to N-lauryl trilethylenetetramine; (3) A polyetherpolyol compound obtained by adding 2 moles of butylene oxide to N octylpropylenediamine, followed by an addition of 8 moles of ethylene oxide; (4) A polyetherpolyol compound obtained by adding 5 moles of ethylene oxide to laurylamine;; (5) A polyetherpolyol compound obtained by adding 3 moles of propylene oxide to oleylbutylamine, followed by an addition of 12 moles of ethylene oxide; (6) A polyetherpolyol compound obtained by adding 6 moles of ethylene oxide to cyclohexylamine; (7) A polyetherpolyol compound obtained by adding: 18 moles of ethylene oxide to the amide of a polymeric acid (dimeric acid/polymeric acids of trimeric acid and up=8/2) of oleic acid; and (8) A polyetherpolyol compound obtained by adding 3 moles of propylene oxide to the amide of a polymeric acid (dimeric acid/polymeric acids of trimeric acid and up=7/3) of fatty acids derived from toll oil, followed by a further addition of 20 moles of ethylene oxide.

Note: 2 Phosphoric acid compounds or boric acid: (1) Phosphoric acid; (2) Butylphosphonic acid; (3) Boric acid; and (4) Hydroxyethanedisulfonic acid, Note: 3 Antioxidant: 2,4-di-t-butyl-t-cresol.

Note: 4 Emulsifier: Polyoxyethylenenonyl Phenyl Ether (HLB: 7.8) (Results) TABLE 6 Metal-working Seizure-resistant Oil Composition Load (Ibs.) invention Product No.

25 1500 26 1750 27 1500 28 1750 29 1750 30 2000 31 1750 32 2000 33 1750 34 1750 35 1500 36 1750 37 1750 38 2000 39 1750 40 1750 41 1500 42 1500 43 1750 44 1750 45 1750 46 2000 47 1500 48 1750 Comparative Product No.

7 1250 8 1000 9 1000 EXAMPLE 5 With respect to metal-working oil compositions prepared in Example 4, their seizure loads were measured in the same manner as in Example 2. Results are given in Table 7.

TABLE 7 Metal-working Seizure Load Oil Composition (kg/cm2) Invention Product No.

25 9.0 26 8.5 27 8.0 28 8.5 29 9.5 30 10.5 31 11.5 32 11.0 33 8.0 34 7.5 35 7.5 36 8.5 37 9.0 38 9.0 39 9.0 40 8.5 41 8.0 42 8.0 43 9.0 44 9.0 45 9.0 46 9.0 47 7.5 48 7.5 Comparative Product No.

7 8.0 8 5.5 9 5.0 EXAMPLE 6 Test on Adhered Amounts Each metal-working oil composition was diluted with water to a concentration of 3% and was then heated to a temperature of 600C. It was then agitated at 10,000 rpm for 60 minutes in a homogenizer, thereby preparing a test sample. The coating of the test sample was effected by heating a surface-cleaned steel plate (50x 150x0.2 mm) to a temperature of 1 500C and then spraying the test sample for 2 seconds at a spray amount of 500 ml/min (pressure: 1 kg/cm2) by means of a gear pump.

The measurement of the adhered amount was carried out by extracting the steel plate, which has been coated with the test sample, with a solvent.

By the way, several types of metal-working oil compositions were chosen from the invention products used in Example 4 and 5 for use in the present test on adhered amounts.

Results are shown in Table 8.

TABLE 8 Metal-working Adhered Amount Oil Composition (9/m2) Invention Product No.

25 1.5 28 1.3 32 1.2 33 1.3 36 1.2 39 1.1 42 1.2 44 1.4 48 1.3 Comparative Product No.

7 0.9 8 0.8 9 0.6

Claims (13)

1. A metal-working oil composition containing as essential components the following components (A) and (B): (A) one or more lube-oil components selected from the group consisting of oils and fats, minteral oils and fatty acid esters; and (B) one or more polyetherpolyol-type dispersant components selected from the following groups (a) to (d):: (a) polyetherpolyols and polyetherpolyol derivatives having molecular weights of 300 to 600,000 and obtained respectively by adding alkylene oxides to polyalkyleneimines and derivatives thereof containing 6 to 200 nitrogen atoms; (b) polyolpolyether derivatives obtained respectively by adding alkylene oxides to polyalkylenepolyamine and derivatives thereof; (c) polyolpolyether derivatives obtained respectively by adding alkylene oxides to alkyl- and alkylaryl-amines and derivatives thereof and having molecular weights of 200 to 100,000; and (d) polyetherpolyol derivatives obtained respectively by adding alkylene oxides to carboxylic acid amides and derivatives thereof and having molecular weights of 200 to 100,000.

2. A metal-working oil composition according to Claim 1, wherein in the component (B) each of the polyalkyleneimines is a polyethyleneimine which continuously contains, in its molecule, at least five moieties represented individually by the following formula (I):

at least one of said five moieties being a moiety represented by the following formula (all):

has OH and/or NH2 groups at least one end thereof, and contains 6 to 100 nitrogen atoms.

3. A metal-working oil composition according to Claim 1, wherein in the component (B) each of the polyalkylenepolyamine and derivatives thereof contains OH and/or NH2 groups at at least one end thereof and 2 to 100 nitrogen atoms.

4. A metal-working oil composition according to Claim 1, wherein in the component (B) each of the alkyl- and alkylaryl-amines contains 4 to 22 carbon atoms.

5. A metal-working oil composition according to Claim 1, wherein in the component (B) each of the carboxylic acid amides is a carboxylic acid amide containing 4 to 22 carbon atoms, or a polymerized acid amide such as the dimeric or trimeric acid thereof.

6. A metal-working oil composition according to Claim 1, wherein in the component (B) each of the alkylene oxide is ethylene oxide or a mixture of ethylene oxide and one or more compounds selected from the group consisting of propylene oxide, butylene oxide and styrene oxide.

7. A metal-working oil composition according to Claim 1, wherein the alkylene oxide amounts to 3 to 80 wt% of the component (B).

8. A metal-working oil composition according to Claim 1, wherein components other than the one or more lube-oil components account for 0.1 to 20 wt% of the whole composition.

9. A metal-working oil composition containing as essential components the following components (A), (B) and (C): (A) one or more lube-oil components selected from the group consisting of oils and fats, mineral oils and fatty acid esters; (B) one or more polyetherpolyol-type dispersant components selected from the following groups (a) to (d):: (a) polyetherpolyols and polyetherpolyol derivatives having molecular weights of 300 to 600,000 and obtained respectively by adding alkylene oxides to polyalkyleneimines and derivatives thereof containing 6 to 200 nitrogen atoms; (b) polyolpolyether derivatives obtained respectively by adding alkylene oxides to polyalkylenepolyamine and derivatives thereof; (c) polyolpolyether derivatives obtained respectively by adding alkylene oxides to alkyl- and alkylaryl-amines and derivatives thereof and having molecular weights of 200 to 100,000; and (d) polyetherpolyol derivatives obtained respectively by adding alkylene oxides to carboxylic acid amides and derivatives thereof and having molecular weights of 200 to 100,000, and (C) one or more compounds selected from phosphoric acid compounds and boric acid.

10. A metal-working oil composition according to Claim 9, wherein in the component (C) each of the phosphoric acid compounds is either one of the following compounds (i) to (v): (i) phosphoric acid and phosphorous acid as well as thio compounds and ester compounds thereof; (ii) mono- and di-phosphoric acid esters containing respectively alkyl, alkylaryl and aryl groups which contain individually at least one hydroxyl group as well as thio compounds thereof; (iii) mono- or di-phosphonic acids which contain respectively alkyl groups containing 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio compounds thereof, as well as derivatives thereof; (iv) mono- or di-phosphinic acids which contain respectively alkyl groups having 1 to 8 carbon atoms, alkylaryl groups and aryl group and thio compounds thereof, as well as derivatives thereof; and (v) mono-, di- and tri-phosphonic acids containing one or more nitrogen atoms.

11. A metal-working oil composition according to Claim 9, wherein the component (C) is contained in an amount of 0.1 to 50 wt% based on the component (B).

12. A composition as claimed in claim 1 and substantially as described in any one of the specific examples hereinbefore set forth.

13. Each and every novel embodiment herein set forth taken separately or in combination.